ethyl (5E)-3-oxooct-5-enoate | 253451-17-1

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 酮酸及其衍生物
• 英文名称: ethyl (5E)-3-oxooct-5-enoate
• 英文别名: (E)-ethyl 3-oxooct-5-enoate
• CAS: 253451-17-1
• 化学式: C₁₀H₁₆O₃
• 分子量: 184.235
• InChiKey: MZLHEOCTDABEKP-AATRIKPKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.86
• 重原子数：
  13.0
• 可旋转键数：
  6.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  43.37
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  ethyl (5E)-3-oxooct-5-enoate 在 sodium tetrahydroborate 、 正丁基锂 作用下， 以 四氢呋喃 、 乙醇 、 二氯甲烷 为溶剂， 反应 0.17h， 生成 (7E)-3-oxo-5-(1,1,2,2-tetramethyl-1-silapropoxy)dec-7-enenitrile
  参考文献：
  名称：

  Unsaturated Oxo−Nitriles:  Stereoselective, Chelation-Controlled Conjugate Additions

  摘要：

  Addition of Grignard reagents to the unsaturated oxo-nitrile 10 (4-hydroxy-4-methyl-6-oxocyclohex-1-enecarbonitrile) provides conjugate addition products with virtually complete stereocontrol. Mechanistic evidence supports a chelation-controlled conjugate addition via alkylmagnesium alkoxide inter mediates. Diverse Grignard reagents having sp(3)-, sp(2)-, and sp-hybridized carbons react with comparable efficiency, with even sterically demanding nucleophiles adding with complete stereocontrol. Unsaturated oxo-nitriles that are incapable of chelation afford diastereomeric conjugate addition products through an unusual boatlike transition state. Collectively, these reactions illustrate the complementary stereoselectivity of chelation-controlled conjugate additions to hydroxylated, unsaturated oxo-nitriles and stereoelectronically controlled conjugate additions to enones.

  DOI：

  10.1021/jo9909709
• 作为产物：
  描述：

  反式-3-己烯酸 在 草酰氯 、 N,N-二甲基甲酰胺 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 2.5h， 生成 ethyl (5E)-3-oxooct-5-enoate
  参考文献：
  名称：

  Unsaturated Oxo−Nitriles:  Stereoselective, Chelation-Controlled Conjugate Additions

  摘要：

  Addition of Grignard reagents to the unsaturated oxo-nitrile 10 (4-hydroxy-4-methyl-6-oxocyclohex-1-enecarbonitrile) provides conjugate addition products with virtually complete stereocontrol. Mechanistic evidence supports a chelation-controlled conjugate addition via alkylmagnesium alkoxide inter mediates. Diverse Grignard reagents having sp(3)-, sp(2)-, and sp-hybridized carbons react with comparable efficiency, with even sterically demanding nucleophiles adding with complete stereocontrol. Unsaturated oxo-nitriles that are incapable of chelation afford diastereomeric conjugate addition products through an unusual boatlike transition state. Collectively, these reactions illustrate the complementary stereoselectivity of chelation-controlled conjugate additions to hydroxylated, unsaturated oxo-nitriles and stereoelectronically controlled conjugate additions to enones.

  DOI：

  10.1021/jo9909709

文献信息

• Synthesis of 1,4-Diazepanes and Benzo[<i>b</i>][1,4]diazepines by a Domino Process Involving the <i>In Situ</i> Generation of an Aza-Nazarov Reagent
  作者：Swarupananda Maiti、Marco Leonardi、Ángel Cores、Giammarco Tenti、M. Teresa Ramos、Mercedes Villacampa、J. Carlos Menéndez

  DOI：10.1021/acs.joc.0c01774

  日期：2020.9.18

  A step- and atom-economical protocol allowing the synthesis of 1,4-diazepanes and also tetrahydro- and decahydro-1,5-benzodiazepines is described. The method proceeds from very simple starting materials such as 1,2-diamines and alkyl 3-oxohex-5-enoates and can be performed under solvent-free conditions in many instances. The key event of this process was the generation in situ of an aza-Nazarov reagent

  描述了一种步骤和原子经济的方案，其允许合成1,4-二氮杂庚烷以及四氢-和十氢-1,5-苯并二氮杂pine。该方法从非常简单的起始原料，例如1,2-二胺和3-氧杂己基-5-烯酸烷基酯出发，在许多情况下可以在无溶剂条件下进行。该过程的关键事件是aza-Nazarov试剂的原位生成及其随后的分子内aza-Michael环化。还建立了反应的分子间形式，并将其用于吡咯并[1,2- a ] [1,5]重氮骨架的第一个实例的合成。